Automatic assignment of absolute configuration from 1D NMR data.

[reaction: see text] Opposite enantiomers exhibit different NMR properties in the presence of an external common chiral element, and a chiral molecule exhibits different NMR properties in the presence of external enantiomeric chiral elements. Automatic prediction of such differences, and comparison with experimental values, leads to the assignment of the absolute configuration. Here two cases are reported, one using a dataset of 80 chiral secondary alcohols esterified with (R)-MTPA and the corresponding (1)H NMR chemical shifts and the other with 94 (13)C NMR chemical shifts of chiral secondary alcohols in two enantiomeric chiral solvents.

Studies in 3-oxy-assisted 3-aza cope rearrangements.

On thermolysis appropriately substituted N-silyloxy-N-allyl enamines undergo smooth 3,3-sigmatropic rearrangments to the corresponding N-silyloxy imino ethers.